Excess volumes and isentropic compressibilities of binary mixtures of di- n -butylamine with iso-alkanols at 303.15 K

Volumes of mixing and deviations in isentropic compressibility for binary mixtures of di-n-butylamine with iso-propanol, iso-butanol and iso-pentanol were measured at 303.15 K. The excess volumes and deviations in isentropic compressibility are negative over the entire range of mole fractions in all the systems. The results point out that there is a strong H-bond interaction between unlike molecules     

Speed of sound,isentropic compressibilities and viscosities of ternary non-electrolyte solutions at 303.15 K

Measurements of ultrasonic speeds, isentropic compressibilities and viscosities were carried out for six ternary mixtures namely dimethylsulphoxide (1) + 1,2-dichlorobenzene (2) + 1-alkanols (3) at 303.15 K. The 1-alkanols include 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol and 1-octanol. The ultrasonic speeds of these ternary mixtures were also evaluated on the basis of Jacobson's free length theory and Schaaff's collision factor theory. From the viscosity data, deviations in viscosity and interaction parameters for various models were also calculated. An attempt has also been made to explain the nature of intermolecular interactions in the light of deviation in isentropic compressibilities and interaction parameter.     

Densities,speeds of sound and isentropic compressibilities of binary and ternary mixtures containing benzene,cyclohexane and hexane at 298.15 K

Densities, ϱ, and speeds of sound, u, have been measured for the ternary mixture {benzene + cyclohexane + hexane} and the corresponding binary mixtures {benzene + cyclohexane}, {benzene + hexane} and {cyclohexane + hexane}, at the temperature 298.15 K. Using these results, the isentropic compressibilities, κ_s, the excess isentropic compressibilities, κ_s^E, and the speeds of sound deviations, Δu, have been calculated for both the binary mixtures and the ternary system. Excess isentropic compressibilities, κ_s^E, and the speeds of sound deviations, Δu, have been fitted to the Redlich-Kister equation in the case of binary mixtures, while the equation of Cibulka was used to fit the values relating to the ternary system. The empiric equations of Redlich-Kister, Tsao-Smith, Kohler and Colinet have been applied in order to predict the κ_s^E and Δu of ternary mixtures from the binary contributions.     

Speeds of sound and isentropic compressibilities of (n-alkoxyethanols + toluene) at T = 298.15 K

Speeds of sound u at the temperature 298.15 K for six ( n -alkoxyethanol  +  toluene) were measured over the whole composition range. The n -alkoxyethanols were 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol, and 2-(2-butoxyethoxy)ethanol. Excess molar volumes V_m^E atT =  298.15 K were also measured for the mixtures of toluene and 2-methoxyethanol, 2-ethoxyethanol, or 2-butoxyethanol over the whole composition range. The speed of sound values were combined with excess molar volumes to obtain values for the product K_{S, m} of the molar volume and the isentropic compressibilityκ_S , and the corresponding excess quantities K_S,m^E were also calculated. The K_S,m^E curves are sigmoid for all mixtures. The deviations of the speeds of soundu^D from their values u^id in an ideal mixture were obtained for all measured mole fractions. These values are compared with the mixing function δu calculated in the paper. The behaviour ofu , u^D, δu, and K_S,m^E as a function of composition and number of carbon atoms in the aliphatic chain of the alkoxyethanol is discussed. Also, theoretical values of the molar isentropic compressibility K_S,m and speed of sound u were calculated using the Prigogine-Flory-Patterson theory with a van der Waals potential energy model and the results compared with experimental data.     

Topological investigations of binary and ternary mixtures: excess isentropic compressibilities

The speed of sound, U_ij 1,3-dioxolane (D) in binary mixtures (ij) with benzene, cyclohexane, n-hexane or n-heptane and U_ijk for 1,3-dioxolane in ternary mixtures (ijk) with the same hydrocarbons have been measured as a function of composition at 298.15 K. The observed data have been utilised to evaluate excess isentropic compressibility of binary, (κ_s^E)_ij and ternary (κ_s^E)_ijk mixtures using density and speed of sound values of the binary and ternary mixtures. The Moelyn-Huggins concept of interaction between the molecular surfaces of the components of a binary mixture [Polymer 12 (1971) 389] has been extended to evaluate excess isentropic compressibility of the studied binary and ternary mixtures. It has been observed that κ_s^E values predicted by a graph-theoretical approach using connectivities of third degree for binary mixtures compare reasonably well with their corresponding experimental values and κ_s^E for ternary mixtures are of the same sign and order of magnitude.     

Experimental densities,refractive indices,and speeds of sound of 12 binary mixtures containing alkanes and aromatic compounds at T = 313.15 K

Densities, speeds of sound, and refractive indices of 12 binary systems of alkanes (hexane, heptane, octane, and nonane) with aromatics (benzene, or toluene, or ethylbenzene) at T = 313.15 K and at atmospheric pressure were determined over the whole composition range, and are presented in this paper. From the experimental results, the derived and excess properties (isentropic compressibility, excess molar volumes, and excess molar isentropic compressibility) at T = 313.15 K were calculated and satisfactorily fitted to the Redlich–Kister equation.     

Studies of viscosity and excess molar volume of binary mixtures: 4. 1-Alkanol + tri-n-butylamine mixtures at 303.15 and 313.15 K

The excess molar volume V^E, the viscosity deviation Δη and the excess Gibbs energy of activation ΔG^1E of viscous flow are calculated from density and viscosity measurements of six mixtures of 1-propanol, 1-butanol, 1-pentanol, 1-heptanol, 1-octanol and 1-decanol with tri-n-butylamine over the entire range of mole fractions at 303.15 and 313.15 K. The values of V^E of all six systems are very large and negative. Except for 1-propanol+tri-n-butylamine, the magnitude of negative deviations in viscosity increases with chain length of alkanol. The results have been explained considering mixed associated species of type A_iB involving alkanol (A) with tri-n-butylamine (B) through OH⋯N bonds. The viscosity data have been correlated with the equations of Grunberg and Nissan, Tamura and Kurata, Hind, McLaughlin and Ubbelohde, Katti and Chaudhri, McAllister, Heric, and of Auslaender.     

Studies of viscosity and excess molar volume of binary mixtures: 2. Butylamine+1-alkanol mixtures at 303.15 and 313.15 K

The excess molar volume V^E, viscosity deviation Δη, excess viscosity η^E, and excess Gibbs energy of activation ΔG*^E of viscous flow have been investigated from the density ρ and viscosity η measurements of eight binary mixtures of butylamine with ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol and decanol over the entire range of mole fractions at 303.15 and 313.15 K. The viscosity data have been correlated with the equations of Grunberg and Nissan [L. Grunberg, A.H. Nissan, Nature 164 (1949) 799–800], Tamura and Kurata [M. Tamura, M. Kurata, Bull. Chem. Soc. Jpn. 25 (1952) 32–37], Hind et al. [R.K. Hind, E. McLaughlin, A.R. Ubbelohde, Trans. Faraday Soc. 56 (1960) 328–334], Katti and Chaudhri [P.K. Katti, M.M. Chaudhri, J. Chem. Eng. Data 9 (1964) 442–443], McAllister [R.A. McAllister, AIChE J. 6 (1960) 427–431], Heric [E.L. Heric, J. Chem. Eng. Data 11 (1966) 66–68], and of Auslaender [G. Auslaender, Br. Chem. Eng. 10 (1965) 196]. The systems studied exhibit very strong cross association through strong O–H⋯N bonding between –OH and –NH₂ groups. As a consequence of this strong intermolecular association, all eight systems have very large negative V^E. Except butylamine+ethanol mixture, the magnitude of negative deviations in viscosity increases with chain length of alkanol.     

Speed of sound and isentropic compressibilities of nonelectrolyte liquid mixtures. I. Binary mixtures containingp-dioxane

The speed of sound was measured for mixtures of p-dioxane with cyclohexane, n-hexane, benzene, toluene, carbon tetrachloride, chloroform, 1,1,2,2-tetrachloroethane, pentachloroethane and ethyl acetate over the whole mole fraction range at 30°C. These data were combined with densities and molar volumes to obtain isentropic compressibilities and Rao's molar sound functions. Excess isentropic compressibilities and excess speeds of sound have also been calculated. The behavior of the present mixtures is discussed in terms of possible molecular interactions and the Prigogine-Flory-Patterson theory of liquid mixtures.     

Enthalpies of mixing of binary and ternary mixtures containing diisopropylether,benzene and cyclohexane at 303.15 K

Enthalpies of mixing H have been measured for liquid binary mixtures of diisopropylether (DIPE)+benzene or cyclohexane and for liquid ternary mixtures diisopropylether+benzene+cyclohexane at 303.15 K and constant pressure using a C80 calorimeter. A Redlich-Kister type equation was used to correlate experimental results.     

Excess molar volumes and deviation in viscosities of binary liquid mixtures of acrylic esters with hexane-1-ol at 303.15 and 313.15 K

Densities and viscosities for the four binary liquid mixtures of methyl acrylate, ethyl acrylate, butyl acrylate and methyl methacrylate with hexane-1-ol at temperatures 303.15 and 313.15 K and at atmospheric pressure were measured over the entire composition range. These values were used to calculate excess molar volumes and deviation in viscosities which were fitted to Redlich–Kister polynomial equation. Recently proposed Jouyban Acree model was also used to correlate the experimental values of density and viscosity. The mixture viscosities were correlated by several semi-empirical approaches like Hind, Choudhary–Katti, Grunberg–Nissan, Tamura and Kurata, McAllister three and four body model equations. A graphical representation of excess molar volumes and deviation in isentropic compressibility shows positive nature whereas deviation in viscosity shows negative nature at both temperatures for all four binary liquid mixtures. Positive values of excess molar volumes show that volume expansion is taking place causing rupture of H-bonds in self associated alcohols. The results were discussed in terms of molecular interactions prevailing in the mixtures.     

Acoustical parameters of toluene + chloroform + cyclohexane mixtures at 303.15, 308.15, and 313.15 K

Ultrasonic velocity, density and viscosity of the ternary mixture of toluene + chloroform + cyclohexane, were measured at 303.15, 308.15, and 313.15 K. The thermodynamically parameters such as adiabatic compressibility (??), intermolecular free length (L _f), free volume (V _f), internal pressure (?? _i ), acoustic impedance (Z), molar sound velocity (R), and molar compressibility (W) have been obtained from the experimental data for all the mixtures, with a view to investigate the exact nature of molecular interaction. Adiabatic compressibility and intermolecular free length decrease with increase in concentration and temperature. The other parameters show almost increasing concentration of solutes. These parameters have been further used to interpret the molecular interaction part of the solute and solvent in the mixtures.     

Excess heat of mixing of binary mixtures of pyridine withn-alkanes at 313.15 K

The molar excess enthalpies of binary mixtures of pyridine with C₆–C₉ n-alkanes have been measured at 313.15 K in the entire composition range. The measuredH ^E values were compared with those calculated by means of the Prigogine-Flory-Patterson theory and by the ERAS method.

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Zusammenfassung Die molaren Überschußenthalpien binärer Mischungen von Pyridin mit C₆–C₉ n-Alkanen wurden bei 313,15 K im ganzen Zusammensetzungsbereich gemessen. Die gemessenenH ^E Werte wurden mit denen verglichen, die mit Hilfe von Prigogine-Flory-Patterson Theorie und nach der ERAS-Methode berechnet wurden.

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313,5 n- (₆-₉) ce . -- (ERAS).

     

Excess volumes of chlorobenzene and bromobenzene with some chloroethanes at 303.15 and 313.15 K

Volume changes on mixing for the binary systems formed by chlorobenzene with 1,2-dichloroethane, 1,1,1-trichloroethane and 1,1,2,2-tetrachloroethane, and by bromobenzene with 1,2-dichloroethane, 1,1,1-trichloroethane and 1,1,2,2-tetrachloroethane, have been measured as functions of composition at 303.15 and 313.15 K. The measured excess volumes are positive over the entire range of composition for the binary systems chlorobenzene + 1,2-dichloroethane and bromobenzene + 1,2-dichloroethane at 303.15 K, and for chlorobenzene + 1,1,2,2-tetrachloroethane at 313.15 K. The measured volumes V^E are negative over the entire composition range for the remaining systems, except for the system chlorobenzene + 1,1,2,2-tetrachloroethane at 303.15 K, where an inversion of the sign of V^E is observed over part of the concentration range.     

Viscometric and volumetric studies on binary mixtures of 1,2-dichloroethane and chlorinated methanes or their binary equimolar mixtures at 303.15 K

Excess viscosities, η^E and molar excess volumes V^E were obtained for binary mixtures of 1,2-dichloroethane and chlorinated methanes and for pseudobinary mixtures of 1,2-dichloroethane and equimolar binary mixtures from chlorinated methanes at 303.15 K. The chlorinated methanes include carbon tetrachloride, chloroform and dichloromethane. Grunberg—Nissan interaction parameter d and interaction energy for flow of activation W_vis were also presented. The relationship between the η^E's and the V^E's has been quantitively considered using Singh's equations. The excess viscosities for all the systems are negative over the entire compositions. There are specific interactions between 1,2-dichloroethane and chlorinated methanes, but the specific interactions are not strong. The interactions of 1,2-dichloroethane with chlorinated methanes decrease in the order: chloroform > dichloromethane > carbon tetrachloride. ‘Pseudochloroform’ has been defined by us for the first time as the equimolar mixture of dichloromethane and carbon tetrachloride.     

Vapor-liquid equilibria of binary mixtures containing methyl tert-butyl ether (MTBE) and/or substitution hydrocarbons at 298.15 K and 313.15 K

An up-to-date high accuracy vapor-liquid equilibrium apparatus (Van Ness' type) for binary and ternary mixtures has been newly built and successfully tested. A program on thermodynamic characterization of binary and ternary mixtures of oxygenate additives and/or hydrocarbons substituting the main classes of constituents of a real gasoline is presented. Some of the early results are reported, discussed and compared with literature data. These systems are the binary mixtures cyclohexane + n-heptane, benzene + cyclohexane and methyl tert-buthyl ether (MTBE) + n-hexane, all have been measured at 313.15 K and the first of them at 298.15 K too.